4-Halo-2,5-dialkyl-benzeneacetonitriles

ABSTRACT

Certain novel alkylated halobenzeneacetonitriles and halomethylbenzeneacetonitriles are effective selective herbicides that can be used in the presence of crops such as corn and soybeans.

United States Patent Martin 4-HALO-2,5-DIALKYL- BENZENEACETONITRILES [75] Inventor: Elmore Louis Martin, Wilmington,

Del.

[73] Assignee: E. I. Du Pont de Nemours and Company, Wilmington. Del.

[22] Filed: Apr. 6, 1972 [21] Appl. No.: 241,836

[52] US. Cl 260/465 G; 71/105 [51 1 Int. C13. C07C 121/66 [58] Field of Search 260/465 G 156] References Cited UNITED STATES PATENTS 31127248 3/1962 Koopmzin et a]. 71/105 3,476,790 11/1969 Burch 260/465 X FOREIGN PATENTS OR APPLICATIONS 760,968 6/1971 Belgium Primary Exuminer-Elbert L. Roberts Assistant ExuminerDo1ph H. Torrence [57] ABSTRACT Certain novel alkylated halobenzeneacetonitriles and halomethylbenzeneacetonitriUes are effective selective herbicides that can be used in the presence of crops such as corn and soybeans.

3 Claims, No Drawings 1 4-HALO-2,S-DIALKYL-BENZENEACETONITRILES BACKGROUND OF THE INVENTION The novel compounds of the present invention are rep resented by the general formula 1) below:

where: I

each of R R R and R independently is hydrogen,

a C C alkyl, a halogen, or a nitro group; each of R and R methyl; Z is halogen; and n is or I; provided that:

a. at most two of R,, R R and R are nitro groups; V b. at most two of R R R and R, are halogens; c. at least one of R RQ, R and R, is hydrogen or halogen; i

independently is hydrogen or Preferred because of higher activity are compounds of formula l wherein both R; and R are hydrogens, and n is 0. Within this preferred class, the most active and the easiest to synthesize are those compounds in I which twoof R R R;,. and R are C 'C alkyl groups,

and the other two are hydrogens.

Compositions containing the benzeneacetonitrilesof this invention can be used in the presence of valuable crops, such as corn and soybeans.

DESCRIPTION OF THE INVENTION Compounds of formula l )(n O) can be prepared l pn cl d. at least two of R Kyls: o each alkyl has at most three carbon atoms in a straight chain from the point of attachment to the aromatic ring; i I l. the nitro groups are not ortho to each other; i g. the ull-iyl groups are not ortho to each other; and h. when 11 is I, both R and R are hydrogens.

R R and R are C -C al by one or more methods using reactions generally known in the art.'Simple halobenzeneacetonitriles can be made, for instance, by halogenation of the corresponding dialkylbenzenes, chloromethylation of the re sulting halodialkylbenz'enes, and replacement of the benzylic chlorine with a eyano group, as shown in the following scheme:

.DMSO 5 ClCHz NCCHz X halogen;

DMSO dimethyl sulfoxide Such reactions are described, for instance, in the following references: G. A. Olah Friedel Crafts and Related Reactions, II, Part 2, Chapter 21. and Fuson and Cdrse. I. Am. Chem. Soc., 60, 2063 (1938) The halobenzeneacetonitrile can be nitrated to a mononitro compound, eg

Nitration is carried out by well-known methods, c0n-' centrated nitric acid being a suitable nitrating agent, cf. Org. Syn. Coll. Vol. II, 254 (11943).

Dihaloben7eneacetonitrilescan be obtained from the dialkylbenzyl halides, as shown below:

DMSO dimethyl sulfoxide Compounds of formula (l)(n l can also be prepared using reactions generally known in the art. The

' simple halomethylbenicneacetonitriles can be made by first halomethylating a benzeneaeetamide and then dehydrating the product with a suitable dehydrating agent such as phosphorous oxychloride or thionyl chloride. For further details see G. A. Olah Friedel Crafts and 3 Related Reactions, II, Part 2, Chapter 21, and A.

Surrey, Org. Syn. Coll; Vol. III, 535 (1955).

The substituted benzeneacetarnides are prepared using reactions generally known in the art. For instance, the dialkylbenzeneacetamides are prepared by chloromethylating the dialkylbenzene, displacing-the benzylic chlorine with a cyano group and then hyd-rolyzing the benzeneacetonitrile to the benzeneacetamide' by the method of Wenner, J. Org. Chem.-, 15, 548 (1950).

; conditions such aslack of ,-rainfall for an extended pereci cases .C'LCH iod after application it is advantageous to soil incorpo- I II (25201 "11 ca cmi act NaCN a zncl mist? H26) DMSO dimethyl sulfoxide An alternate procedure for the preparation of com pounds of formula (1 )(r z l is shown below:

I1 a CHsCOCHr HGCHQ X halogen The halomethylbenzeneacetonitriles may be halogenated to a mono or dihalo compound, e.g.

Halogenation is carried out by well-known methods, iron powder being a suitable catalyst. A good operation procedure is described by Fuson and Corse, J. Am. Chem. Soc. 60, 2063 (1938).

The compounds of this invention are useful as selective pre-plant incorporated, preemergenee, or postemergence herbicides. They provide control of many weeds with excellent selectivity in such crops ascorn, soybeans, wheat, cotton and rice. The compounds are most advantageously applied precmergence, at rates of 0.25 to pounds per acre, dependingon the crop, the weed to be controlled, the soil and environmental conditions and the particular chemical used. Under certain AGE 2 X ca m Weeds controlled include erabgrass (Digitaria spp.), barnyardgrass (Echinoc/zloa crusgalli), junglerice (Eclu'noc'lzloa colonum), foxtail (Setaria spp.), witch- C'daCN C NaN CHQCN grass (Panic-um capillare), goosegrass (Ele usir e indica), pigweed (Amz mintlzus retruflewius), wild mustard (Brassica spp.), curly dock (Rumex crispus), johnsongrass (Sorghum halepense) from seed, cheat (Bromz'ls secalinus), downy brome (Bromus lectorum) and blackgrass (A lopucurus mysuroides It is sometimes advantageous to combine a compound of this invention with another herbicide in order to increase the spectrum of weeds controlled and to minimize the chances of injury to the current or subsequent crops. The exact combination which may be used to the best advantage will depend upon the crop, the weeds to be controlled and the environment in which the crop is growing. The combination which will be most advantageous depends on the crop, the soil, the weeds expected and the climate, but can be readily seleeted by one with ordinary skill in the art. The use of other herbicides in combination with the herbicides of this invention will provide control of a widevariety of broadleaved weeds including ragweed (Ambrosia spp.) lambsquarter (Clzenopudium album morningglory (lpomea spp.) sicklepod (Cassia obtuszfblia), smartweed (Polyganum spp.), flower-of-an-hour (Hibiscus trionum), cocklebur (Xanthium spp.) and.velvetleaf (Abutilon theophrasti), as well as grasses.

The herbicidal compositions of this invention containing mixtures with other herbicides can be formulated as such. Alternatively, the compounds of Formula 1 may be tankmixed with other known herbicides or applied sequentially with other known herbicides.

Among the known herbicides which can be combined with the compounds of Formula 1) are:

' SUBSTITUTED UREAS 3- 3 ,4 -dich loroph enyl 1 1 -c1i rnethy1urea 3-(4-chlorophenyl)-1,1-dimethylurea 3-pheny1-1,1-dimethylurea I 3-( 3,4-clich1orophenyl )-3'-rnethoxy-l 1 -dimethy1urea 3-(4-chlorophenyl )-3-methoxy-l l-dimethylurea 3-( 3 ,4-dichlorophenyl 1 -n-buty1- 1 -meth'ylurea 3-(3,4-dichlorophenyl)-l-methoxy l-rnethylurea 3-(4-chlorophenyl 1 methoxy 1 -methylurea 3-(3,4-dichlorophenyl)-1,1,3 tr'imethylurea 3-( 3 ,4-dichlorophenyl 1 1 -diethylurea 3-(p-chlorophenoxyphenyl 1 1-dimeth'ylurea N-cyclooctyl-N-dimethylurea' 3-(4-chlorophenyl)-1-methyl-1-'( 1-rnethyl-2- propyny1)urea 3-( 4-bromo-3-chlorophenyl 1 -methoxy- 1 methylurea 3-[p-(p-chlorophenoxy )phenyl1-1 ,l-dimetliylurea 3-( 4'trifluoromethy1phenyl 1,1-dimethylurea 3-(4-bromophenyl)- l -methoxy- 1 -methy1urea 3-( hexahydro-4,7-methanoindan-S-yl )-1 1 -dimethylurea i 1-(2-methy1cyc1ohexyl)-3-phcnylurea 3-(p-cumeny1 )-1,l-dimethylurea 1 These ureas can be mixed with the compounds of Formula (1) in weight proportions of from 1:40 to :1, the preferred ratio being 1:12 to 4:1.

SUBSTITUTED TRIAZINES 2-chloro-4,6-bis(ethylamino)s-triaiine 2-chloro-4-ethylamino-6-isopropylamino's-triazine 2-chloro-4,6-bis( methoxypropylarnino )-s-triazine 2-methoxy-4,6-bis( isopropylamino )-s-triazine Z-diethylamino-4-isopropylacetamido-6-methoxy-striazine i I 2-isopropylamino-4-methoxyethylamino-6-methylmercapto-s-triazine 2-methylmercapto-4,6-bis( isopropylamino )-s-triazine 2-methylmercapto-4,6-bis(ethyla mino)-s-triazine 2-methylmercapto-4-ethylamino--isopropylaminos-triazine 2-methoxy-4,6 -bis(ethylamino)-s-triazine 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis(isopropylamino)-s-triazine 2-methoxy -t4,6-bis(isopropylamino)-s triazine 2-ethylamino-4-isopropylamino-6methylmercaptos-triazin'e 2-chl'oro-4-chloropropylamino-o-isopropylamino- 1,3,5-triazine 2,4 bis(isopropylamino)-Gmethylmercapto-striazine i i I I 2-tert-butylamino 4 ethylamino-o rnethylthio-s-tria zine I I I i v i I These triazines can be mixed with the compounds of this invention in the weight proportions of from 1:40 to 10:1, the preferred ratio being 1:12 to 4:l.

PHENOLS I 3,5-dinitro-o-cresol 4,6-dinitro-o-sec-butylphenol and its salts 4,6-dinitro-o-sec amylphenol pentachlorophenol and its salts v These phenols can be mixed with the compounds of this invention in the Weight proportions of from 1:10 to 10:1, the,preferred ratio being 1:5,to 5:1.

SUBSTITUTED URACILS 3-isopropyl-5-bromo-6-methyluracil 5-bromo-3-sec-butyl-6-methyluracil 3-tert-butyl-S-chloro-6 methyluracil 5-chloro-6-methy1-3-neopentyluracil 3-tert-butyl-5-bromo-6-methyluracil 3-isopropyl-5-chloro-6-methyluracil 3-tert-buty1-5-chlor0-6-ethyluracil 3-tert-butyl-5 chloro-o-chloromethyluracil I 3-cyc lohexyl-6-methyluracil 3-cyclohexyl-o-ethyluracil 3-cyclohexyl-6-sec-butyluracil 3 norbornyl-6 methyluracil 3-cyclopentyl-6-methyluracil 3-cyclohexyl-6-isopropyluracil 3-cyclohexyl-5,6-trimethyleneuracil 3-sec-butyl-5,-trimethyleneuracil, 3-isopropyl-5,o-trimethyleneuracil 3-isopropy1-5,6-tetramethy1eneuracil 3-isopropyl-5,o-pentamethyleneuracil 3-cyclohexyl-S-bromouracil 3-cyclohexyl-5-chlorouracil 3-isopropy1-5-bromouraci1 3-secb"'uty1-5-bromouracil 3 sec-btityl-5 chlorouracil Ii-isopropyl-1-trichlorometh.ylthio 5-bromo-6- methyluracil v 3-cyclo liexyl- 1 -tric loromethyIthiO-S-bro mo 6- methyluracil 3-sec-butyl-1-ace ty1-5-bromo-6-methyluracil 3-isopropyl-1-acetyl-5-bromo-6-methyluracil 3-isopropyl-1-trich1orornethylthio- 5-ch1oro-6- methyluracil r These substituted uracils can be mixedwith the com pounds of this invention in the weight proportionsof from 1:80 to 10: 1, the preferred ratio being from 1:20 to 4: 1.

cARBoxYuc ACIDS AND DERIVATIVES (2-methyl-4-chlorophenoxy)acetie acid and its salts and esters (Z-methylA-chlorophenoxy)propionic acid and its salts and esters v 2-(2,4,5-trichlorophenoxy)propionic acid and its salts and esters 2-( 2,4,5-trieh1orophenoxy )ethyl-2 ,Z-dichlbropropionate 4-(2,4dichlorophenoxy)butyric acid and its salts and esters 4-(2-methyl-4-chlorophenoxy)butyric acid and its salts and esters 2,3,o-trichlorobenzyloxypropanol tris( 2,4-dichlorophenoxyethyl )phosphitc Mixed in a 1:80 to 8:1 ratio, preferably a 1:20 to 2:1 ratio.

2,6-dichlorobenzonitrile 3,5dibromo-4-hydroxybenzonitrile Mixed in a 1:40 to 4:1 ratio, preferably a 1:16 to 3:1 ratio.

trichloroacetic acid and its salts Mixed in a 1:8 to 8:1 ratio, preferably a 1:4 to 4:1 ratio. i

2,2-dichloropropionic acid and its salts 2-(a-naphthoxy)-N,N-diethylpropionamide 2-(4-chloro-6-ethylamino-2-ylamino)methylpropionitrile Mixed in a 1:8 to 8:1 ratio, preferably a 1:4 to 4:1 ratio.

N,N-di(n-propyl)thiolcarbamic acid, ethyl ester N,N-di(n-propyl)thiolcarbamic acid, n-propyl ester N-ethyl-N-(n-butyl)thiolcarbamic acid, ethyl ester N-ethyl-N-(n-butyl)thiolearbamic acid, n-propyl ester S-2,3-dichloroallyl-N,N-diisopropylthiolcarbamatc S-2,3,3-trichloroallyl-N,N-di-isopropylthiolcarbamate S propyl-n-butylethylthiocarbamic acid 2-ch1oroallyldithiocarbamate S-ethyl diisobutylthiocarbamate 2chloroallyldiethyldithiocarbamate S-ethyl-N-ethylthiocyclohexanecarbamate Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio.

N-phenylcarbamic acid, isopropyl ester N-(m-chlorophenyl)carbamic acid, isopropyl ester N-(m-chlorophenyl)carbamic acid, 4-chloro-2-butynyl ester N-(3,4-dichlorophenyl)carbamic acid, methyl ester N-( 3,3-dimethylureido )phenyl-tert-butylcarbamate 2,6-di-tert-butyl-p-tolylmethylearbamate Mixed in a 1:8 to 8:1 ratio, preferably a 1:4 to 4:1 ratio.

2,3,o-triehlorophenylacetic acid and its salts Mixed in a 1:4 to 8:1 ratio, preferably a 1:4 to 4:1 ratio.

2-ehloro-N,N-diallylacetamide maleic hydrazide 1,2-dihydropyridazine-3,6-dione 3 ,4-dichloro-2-methacrylanilide 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide 8 N-(butoxymethyl)-2-chloro-2',6-diethylacetanilide 3,5-dinitroN',N'-dipropylsulfanilamide I 2-chloro-N-isopropylacetanilide 3,4-diehloropropionanilide Mixed in a 1:8 to 10:1 ratio, preferably a 1:4 to 5:1 ratio. 1.

4-amino-3,5,6-trichloropicolinic acid Mixed in a 1:100 to 4:1 ratio, preferably a 1:20 to 2:1 ratio.

INORGANIC AND MIXED INORGANIC-ORGANIC SALTS The following salts can be mixed with the compounds of this invention in the listed weight proportions: A.

monoammonium methanearsonate calcium methylarsonate calcium propylarsonate disodium monomethylarsonate octyl-dodecylammoniummethylarsonate dimethylarsinic acid hydroxydimethylarsine oxide Mixed in a 1:8 to 4:1 ratio, preferably a 1:4 to 2:1 ratio.

sodium arsenite potassium cyanate v Mixed in a 1:10'to 20:1 ratio, preferably a 1:5 to 10:1 ratio. C.

lead arsenate calcium arsenate Mixed in a 10:1 to :1 ratio, preferably a 20:1 to 50:1 ratio. D.

sodium tetraborate hydrated, granulated sodium metaborate sodium pentaborate polyborchlorate unrefined borate ore such as borascu Mixed in a 10:1 to 600:] ratio, preferably a 20:1 to 400:] ratio.

ammonium thiocyanate Mixed in a 1:10 to 10:1 ratio, preferably a 1:5 to 5:1 ratio:

sodium chlorate Mixed in a 10:1 to 200:1 ratio, preferably a 15:1 to 100:1 ratio.

ammonium sulfamate Mixed in a 1:1 to 200:1 ratio, preferably a 2:1 to 100:1 ratio.

OTHER ORGANIC HERBICIDES These organic herbicides can be mixed with compounds of this invention in the listed weight proportions:

6,7-dihydrodipyridol 1 ,2-a;2,l -c ]pyra zinediium ion 1,1 '-dimethyl-4,4-bipyridinium ion Mixed in a 1:20 to 10:1 ratio, preferably a 1:10 to 5:1 ratio.

3-amino-l ,2,4-triazole Mixed in a 1:20 to 20:1 ratio, preferably a 1:10 to :1 ratio.

3 ,6-endoxohexahydrophthalic acid Mixed in a 1:10 to :1 ratio, preferably a 1 :4 to 10:1 ratio.

hexachloroacetone Mixed in a 1:8 to 16:1 ratio, preferably a 1:4 to 8:1 ratio. l

diphenylacetonitrile N,N-dimethyl-a,a-diphenylacetamide N,N-di-n-propyl-2,6-dinitro-4-trifluoromethylaniline' N,N-di-n-propyl-Z,6-dinitro-4-methylaniline 2,6-dinitro-N,N-di(2-chloroethy1 )-p-toluidine 4-(methylsulfonyl)-2,6-dinitro-N,N-dipropylaniline N-sec-butyl-4-tert-butyl-2,6-dinitroaniline 3 -chloro- 2-methyl-p-valerotoluidide 1 2-chloro-N-(ethoxymethyl)-6-ethyl-O-acetotoluidide N-buty1-N-ethyl-a,a,oz-trifluo:ro-2,6-dinitro-p-toluidine Mixed in a 1: 10 to 10:1 ratio, preferably a 1:5 to 5:1 ratio.

' 3,3a-dihydro-2-(p-methoxyphenyl)-8H-pyrazolo(5- ,1A)-isoindol-8-0ne 2-[ 3-(4-methoxyphenyl )-5pyrazolyl benzoic acid 2-( 3-phenyl-5-pyrazolyl)benzoic acid Mixed in a 1:20 to 8:1 ratio, preferably a 1:10 to 4:1 ratio. 1

The preparation of representative benzeneacetonitriles of the present invention is illustrated in the fol lowing examples, in which all parts, proportions, and percentages are by weight, unless indicated otherwise.

4-isopropyl-2,6-dinitro-N,N-dipropylaniline 20 Mixed in a 1: 10 to 10:1 ratio, preferably a 1:5 to 5:1 EXAMPLE 1 ratio. 1 i R 2-Bromo l ,4-diisopr opylbenzene O-(2,4-dichlorophenyl)-O-methylisopr py p To a 1-liter flask containing v243 parts of p-diisoprophorflmldothlate pylbenzene, 300 parts of carbon tetrachloride and 2.5 0,0-dilsopropylphosphorodithioate-s ester wlth N- parts of iron powder is added dropwise 240 parts of (z-mercaptoethyl)benZenSulf0nam1de'i bromine and sufficient carbon tetrachloride to make S-ethy1hexahydr0-lH- p Q 180 parts of solution during 7 hours at a temperature of 2,3,5,6-tetrachloroterephthali acid, dlmethyl ester 5C. The solution is decanted from the residual ferric Mixed in a 1:20 to 20:1 ratio, preferably a 1:10 to 10:1 ratio.

2,4-dichlorophenyl-4-nitrodiphenyl ether 2,4-dinitro-4-trifluorornethyldiphenylether bromide and washed twice with 3N HCl. The carbon tetrachloride is removed under reduced pressure. A so lution of 40 parts potassium hydroxide in 200 parts of ethyl alcohol is added and refluxed 0.5 hr. The solution is poured into water, separated, washed with dilute hy- MiXed in a 1320 to 1011 ratio, Preferably a 1110 to 511 drochloric acid, dilute sodium bisulfite solution and ratio. water, and dried. The solvent is removed and the 2- H. bromo-1,4-diisopropylbenzene distilled, bp 142C at N-1naphthylphthalamic acid and its salts 25 mm, n 1.5292.

Mixed in a 1:8 to 20:1 ratio, preferably a 1:4 to 10:1 By substituting the following alkylbenzenes for p ratio. diisopropylbenzene, the following haloalkylbenzenes I. are made: i

TABLE 1 Starting Material Product p-isobutylisopropylbenzene m-isobutylisopropylbenzene p-isobutylpropylbenzene p-sec-butylisobutylbenzene m-sec-butylisobutylbenzene p-ethylisohutylbenzene p-di-secbutylbenzene m-di-sec-butylbenzene p-tcrt-butylisopropylbenzene mtert-butylisobutylbenzene m-diisopropylbenzene p-diisobutylbenzene ditert-butylbenzene p-tei1butylethylbenzene p-sec-butylethylbenzene p( 1,2-dimethylpr0pyl)ethylbenzene p-( 1,2-dimethylpropyl )propylbenzene p-( l,Z-dimethylpropyl)isobutylhenzene p-te rt-butylisobutylbenzene p-ethyl-tert-pentylbenzene 2-fluoro-1,4-diisobutylbenzene Z-fluoro-l ,S-diisopropylbenzene 4-( 1,2 dimethylpropyl)l-ethyl-Zfluorobenzene m-ethyl-tert-pentylbenzene p-methyl-( 1,1,2.2-tetramethylpropyl)benzene p-ethyl-( 1,1,2,2-tetramethylpropyl)benzene m-diethylbenzene m-diisobutylbenzene p-ethylneopentylbenzene 3-bromo-4-isobutylisopropylbenzcnc 4-bromo3-isobutylisopropylbenzcne 2-bromo 4-isobutylpropylben2ene 2-bromo-4-sec-butylisobutylbenzene 1-bromo4-sec-butyl-2-isobutylbenzene 2-bromol -ethyl-4-isobuty1benzene 2-bromo- 1 ,4-di-sec-butylben2ene 1-bromo-2,4-di-sec-butylhenzene 2-bromo-4-butylisopropylbenzene l-bromo-4-tert-butyl-2-isobutylbenzene 4 bromo- 1 ,3-diisopropylbenzene Z-bromo-l ,4-diisobutylbenzene, bp 72C at 0:1. :mm

1 ,4di-tert-butyl-2-chlorobenzene 2-bromo-4-tert-butylethylbenzene 2-bromo-4-sec-butylethylbenzene 2-bromo4-( 1,2-dimethylpr0pyl )ethylbenzene 2-bromo-4-( 1 .Z-dirnethylpropyl )propylbenzene 2-bromo-4-( l ,Z-dimethylpropyl )isobutylbenzene 2-bromo-4-tert-butylisobutylbenzenc 2-bromol ethyl 4-tert-pentylbenzene 5-bromo2-fluorol ,4-diisobutylbenzene 4-bromo-2-fluoro l ,S-diisopropylbenzene 5bromo-4-( 1,2-dimethylpropyl 1 -ethyl-2-fl uorobenzene 4-bromo-3-ethyl-tert-pentylbenzene 2-bromol -methy1-4-( l,1,2.2-tetramethylpropyl)benzene 2-bromo- 1-ethyl-4-( 1, 1 ,2,2-tetramethylpr0pyl )benzene 2-bromo-l .3-diethylbenzene 2-bromo-1 ,3-diisobutylbenzene 3-bromo4-ethylneopentylbenzene EXAMPLE 2 2-Fluoro-l,4-diisobutylbenzene (Org. React. Vol V, p 203) To 124 partsof 6N hydrochloric: acid is added 48.8 parts of 2,5-diisobutylaniline. The mixture is cooled to and a cold solution of 17.3 parts of sodium nitrite in water is added slowly, keeping temperature at 0. A cold solution of 35 parts of ammonium fluoroborate in 120 parts of water is added with vigorous stirring. After one half hour, the precipitate is collected, washed with parts cold 5% ammonium fluoroborate solution, parts cold methanol, and ether. The 2,5-diisobutylben- Zenediazonium fluoroborate is air dried. The salt is placed in a flask with tube connecting to a second cooled flask and heateduntil decomposition begins. Sufficient heat to maintain gentle decomposition is continued. When decomposition is complete, the 2- EXAMPLE 3 4-Bromo-2,5-diisopropylbenzyl Chloride In a flask is placed 36 parts of 2-bromol ,4-diisopropylbenzene, 3O parts of paraformaldehyde and 20 parts of zinc chloride. A stream of dry hydrogen chloride is passed in with stirring, and the temperature rises to C. The temperature is maintained at 65C for 3 hours and is increased to C. Additional amounts of 15 parts of paraformaldehyde and 15 parts of zinc chloride are added, and the reaction is continued at for a total time of 6.5 hrs. The mixture is cooled and washed with hydrochloric acid, dilute sodium bicarbonate, and water. After drying, the 4-bromo-2,5-diisopropylbenzylchloride is distilled, bp 9l-93C at 0.5

By substituting the following haloalkylbenzenes for 2-br0mo-l ,4 -diisopropylbenzene, the following haloalkylbenzyl halides are made.

TABLE III Starting Material 3-bromo-4-isobutylisopropylbenzene 3-bromo-4-isobutylisopropylbenzene 2-bromo-4-isobutylpropylbenzene 2-bromo-4-sec-butylisobutylbenzene l-bronio-4-sec-butyl-2-isobutylbenzene 2-bromol -ethyl-4-isobutylbenzene 2bromol ,4-di-sec-butylbenzene l-bromo-2,4-di-sec-butylbenzene 2bromo-4-tert-butylisopropylhenzene 4-te rtbutyl-2-chloroisopropylbenzene 4-bromol ,3-diisopropylbenzene 2-bromol ,4-diisobutylbenzene 5-bromo-2-fluor0 l ,4-diisobutylbenzene 4-bromo-2-fluorol ,5-diisopropylbenzene benzene 4-bromo-3-ethyl-tert-pentylbenzene Product fluoro-l,4-diisobutylbenzene is taken up in ether,

5-bromo-4-ethyl-2tert-pentylbenzyl chloride In some cases, chloro methylation of the bromoalkylwashed with dilute sodium hydroxide and water, and 40 benzenes gives mixtures of isomers. These may be sepadried. Removal of the ether gives Z-fluoro-l ,4-diisobutylbenzene which can be purified by distillation under reduced pressure.

In a similar manner the following compounds are prepared:

TABLE ll rated by careful distillation or by chromatography, but usually the mixture is used in subsequent reaction. The following compounds give the indicated mixtures when chloromethylated:

Starting Material Product 2,4-diisopropyluniline 5-( LZ-dimethylpropyl )-2-ethylaniline 2 ethyl-5-( l,l,2,2-tetrumethyl )aniline 2,5-diisopropylaniline 2-isohutyl-5-isopropyluniline 5-tert-hutyl-2-isopropylaniline TABLE IV Starting Material Product I 2-bromol ,4-di-tert-butylbenzene 2-bromo4tert-butylethylbenzene 2-bromo-4-sec-butylethylbenzenc 2-bromo-4-( LZ-dimethylpropyl )ethylherizene 2-bromo4-( l ,2-dimethylpropyl )propylbenzene 3-bromo-2,S-di-tert-butylbenzyl chloride 7 4-bromo-2,5-di-tert-butylbenzyl chloride 3-bromo-5-ten-butyl-2-ethylbenzyl chloride 4-bromo-2-tert-butyl-S-ethylbenzyl chloride,

Table lV- Continued Starting Material 2-bromo-4-( l,Z-dimethylpropyl)isobutylbenzene Product 3-bromo-5-( l,2 dimethylpropyl)-2-isobutylbenzyl chloride 4 bromo-2-( l-,2-dimethylpropyl )5-isobutylbenzyl chloride 2-bromo4-tert-butylisobutylbenzene 3-bromo-5-tert-butyl-2-isobutylbenzyl chloride 4-bromo-2-tert-butyl-5isobutylbenzyl chloride 2-bromo l -ethyl-4tert-pentylbenzene lbromo-Z-ethyl-S-tert-pentylbenzyl chloride 4-bromo-5-ethyl-2-tert pentylbenzyl chloride Z-bromol -ethyl-4-( l-ethyll -methylpropyl )benzene 3-bromo-2-ethyl-5 I-ethyll -methylpropyl )benzyl chloride 3-bromo'4-ethylneopentylbenzene 3-bromo-2-ethyl-5-neopentylbenzyl chloride 4-bromo-5ethyl 2-neopentylbenzyl chloride 2-bromo-l ,3-diethylbenzene 3-bromo-2,4-diethylbenzyl chloride 4-bromo-3,5-diethylbenzyl chloride 2bromo-1,3-diisobutylbenzene 3-bromo-2i4 diisobutylbenzyl chloride 4-bromo 3,S-diisobutylbenzyl chloride TABLE VI Starting Material Product 4-bromo-2-ethyl-5risobutylbenzyl chloride 4-bromo-5-( 1,2-dimethylpropyl)-2-propylhenzyl chloride 3-iodo2,6-diisopropyl 4 methylbenzyl chloride 4-bromo-2 isopropyl 5-( l,l,2,2tetramethylpropyl benzyl chloride .4bromo-5-isobutyl2-isopropylbenzyl chloride 3-bromo-2,b-di-tert-butyl-4-methylbenzyl chloride 4-bromo-2-chlortro-ethyl-3-isobutylbenzyl chloride 4-hromo-2-chloro-3 l ,Z-dimethylpropyl )-6-propylbenzyl chloride 3,5-diiodo-2,6-diisopropyl4-methylbenzyl chloride 4-hromo-2-chloro-(J-isopropyl-3-( l, l ,2,2-tctru methylpropyhh'enzyl chloride 4bromo-2-chloro-3-isobutyl-6-isopropylbenzyl chloride 3-bromo-2,o-di tcrt-hutyl-5-chloro-4methylbenzyl chloride EXAMPLE 4 2,4-Dibromo-3,o-diisobutylbenzyl Chloride obtained:

For unsymmetrical alkylbeznzenes, a different ultimate product is obtained if one first chloromethylates and then brominates.

EXAMPLE 6 2-Is0butyl-5-isopropylbenzyl Chloride In a flask there are placed 176 parts of p-iso- TABLE V Starting Material Product 2,5-dipropylbenzyl chloride 2-isobutyl-S-isopropylbenzyl chloride 2,5-diisopropylbenzyl'chloride 2,5-di-tert'butylbenzyl chloride 2,5 di-sec-butylbenzyl chloride 2,4-dibromo-3,-dipropylbenzyl chloride 2 4-dibromo-6-isobutyl-3-isopropylbenzyl chloride 2.4-dibromo-3,6-diisopropylbenzyl chloride 2,4-dibromo-3,o-di-tert-butylbenz'yl chloride 2,4-dibrom0-3,6-di-sec-blitylbenzyl chloride EXAMPLE 5 4-Bromo-2 chloro-3 ,6-diisopropylbenzyl Chloride To a solution of 29 parts of 4-bromo-2,5-diisopr0pylbenzyl chloride in parts of carbon tetrachloride there is added 1.0 part of iron powder. To the mixture, cooled to 0 and stirred, there is added 7.8 parts of chlorine during 2 hr Stirring is continued for 2 hours; the solution is washed with dilute hydrochloric acid, sodium bicarbonate solution, and water. After drying, the carbon tetrachloride is removed, and 4-bromo-2- chloro-3,o-diisopropylbenzyl chloride is recovered.

By replacing 4-bromo-2,5-diisopropylbenzyl chloride with the following benzyl chlorides, these products are obtained:

propylisobutylbenzene, 15. parts of paraformaldehyde, and 15 parts of zinc chloride. A stream of hydrogen chloride is passed into the mixture, and the temperature is increased to 65C. After the mixture is saturated with hydrogen chloride, stirring is continued at 75C for 3 hours. The mixture is cooled and washed with hydrochloric acid, sodium bicarbonate solution, and water. After drying, the product is distilled. The first fraction is the unchanged starting material; the higher boiling material,'7580C at 0.05 mm, is the desired 2 isob utyl-5-isopropylbenzyl chloride.

By the useof the indicated starting alkylbenzene in the same molar amount as in the above example, the following compounds are prepared:

TABLE VII Starting Material Product m-isobutylisopropylbenzene 2-isobutyl-4-isopropylhenzyl chloride p-isohutylpropylbenzene 5-isobutyl-2-pr0pylbenzyl chloride m-isobutylpropylbenzene 4-isobutyl-2-propylbenzyl chloride p-sec-butylisobutylbenzene 5-see-hutyl-2-isobutylhenzyl chloride m-see-butylisobutylbenzene 4-sec-hutyl-2-isohutylhenlyl chloride p-ethylisobutylbenzene 2-ethyl-5-isobutylhenzyl chloride m-tert-butyleumcne 4tert-butyl-2-isopropylhcnzyl chloride p4ert-butylethylbcnzene 5-tert-butyl-2-ethylbenzyl chloride p-sec-butylethylhcnzene fi-sec-hutyl-Z-ethylbenzyl chloride p-( l,Z-dimethylpropyl)ethylhenzene 5-( l,Z-dimethylpropyl)-2-ethylbenzyl chloride p-( l,Z-dimethylpropyl)propylbenzene 5-( l.2-dimethylpropyl)-2-propylbenzyl chloride p( l ZdimethyIprOpyI)isohutylhenzene 5-( l.2-dimethylpropyl)-2-isohutylbenzyl chloride p-tert-butylisobutylhenzene S-tert-butyl-Z-isobutylbenzyl chloride pethyl-tert-pentylbenzenc Z-ethyl-S-tcrt-pentylbenzyl chloride m-diethylhenzene 2,4-dicthylbenzyl chloride m-diisobutylbenzene 2,4-diisohutylbenzyl chloride m-dipropylhenzene l o-dipropylbenzyl chloride m-diisobutylhenzene 2,6-diisobutylbenzyl chloride p-ethyll l 2-trimethylpropyl )benzene 2-ethyl-5-( l, l .Z-trimethylpropyl )benzyl chloride p-propyll l 2.2-tetramethylpropyl )benzene 2-propyl-5-( l l 2,2-tctramethylpropyl )benzyl chloride EXAMPLE 7 bromo-2-isobutyl-5-isopropylbenzyl chloride distilled 4-Bromo-2-isobutyl-5-isopropylbenzyl Chloride under reduced pressure.

25 In a similar manner, using the designated benzyl chlol' d22 't f2-' bt-5-' In flask are p ace 5 par S 0 u y! lsopro ride, the following compounds are made:

pylbenzyl chloride, 300 parts of carbon tetrachloride TABLE Vlll Starting Material I Product 2-isohutyl-4-isopropylhcnzyl chloride S-bromo-2-isobutyl-4isopropylbenzyl chloride S-isohutyI-Z-propylbenzyl chloride 4-bromo-5-isobutyl-2-propylbenzyl chloride 4-isobutyl-2-propylhenzyl chloride 5-bromo-4-isohutyl-2'propylbenzyl chloride 5-sec-butyl-2-isobutylhenzyl chloride 4-hromo-5-sec-butyl-2-isohutylbenzyl chloride 4-sec-butyl-2-isobutylbenzyl chloride 5-bromo-4-secbutyl-Z-isobutylbenzyl chloride 2-ethyl-5-isobutylbenzyl chloride 4-hromo-2-ethyl-5-isobutylhenzyl chloride 5-tertbutyl'2 isopropylhcnzyl chloride 4-hromo-5-tert-hutyl-2-isopropylbenzyl chloride 4-tert-butyl-2-isopropylbenzyl chloride 6-hromo-4-tert-butyl-2-isopropylbenzyl chloride 2,4-diisopropylbenzyl chloride 5-chloro-2,4-diisopropylbenzyl chloride 2,4-diisopropylbenzyl chloride S-iodo-Z,4-diisopropylbenzyl chloride 2-ethyl-5-( l. l ,Z-trimcthylpropyl )henzyl chloride 4-hromo-2-ethyl-S-( l l .Z-trirnethylpropyl )bcnzyl chloride 2-propyl-5-( l. l ,ZJ-Ietramethylpropyl )henzyl 4-hromo-2-propyl-5-( l l 2,2-tetramethylprnpyl chloride benzyl chloride and 2.5 parts of iron powder. Bromine (160 parts) in In some cases, bromi'nation of the chloromethylalkyl- 100 parts of carbon tetrachloride is added dropwise benzenes gives mixtures of isomers which can be sepa- 45 durin 7 hr. The Solution is washed twice with hydror e y c r f isti l i n r r m gr p y, but chloric acid then with sodium bicarbonate solution, dially the ixtur is adequate for th intended purlute sodium bisulfite solution, and water. The solution p se. The following compounds give the indicated mixis dried, the carbon tetrachloride removed and the 4- ture when brOminated:

TABLE lX Starting Material Product S-tert-butyl-Z-ethylbcnzyl chloride 4-hromo-S-tert-hutyl-Z-ethylbenzyl chloride 3-hromo-5-terthutyl-2-ethylhcnzyl chloride S-Sec-hutyl-2-ethylhenzyl chloride 4-bromo-4-see-butyl-2-ethylhenzyl chloride 3-bromo-S-sec-hutyl-Z-ethylhenzyl chloride 5-( l,Z-dimethylpropyl)-2-ethylhenzyl chloride 4-hromo-5-( l.2-dimethylpropyl)-2-ethylbenzyl chloride 3-hromo-5-( LZ-dimethylprom-l )-2-eth vlhen7.yl

chloride 5-( l.Zdimethylpropyl)-2-propylhenzyl chloride 4-hromo-5-( l,2-din1ethylpropyl)-2-propylhenzyl chloride 3-bromo-5-( l .Z-dimethylpropyl J-Z-propylbenzyl chloride 5-( LZ-dimethylpropyl )-2-isohutylhenzyl chloride 4-hromo-5-( l ,Z-dimethylpropyl )-2-isohutylhenzyl chloride 3-bromo-5-( LZ-dimcthylpropyl )-2-isohutylhenzyl chloride S-tert-hutyl-Z-isobutylhenzyl chloride 4-bromo-5-tcrthutyl-Z-isohutylbenzyl chloride 3-bromo-S-tert-hutyl-2-isobutylhcnzyl chloride Z-ethyl-S-tert-pentylbcnzyl chloride 4-bromo-2-ethyl-5-tert-pentylhenzyl chloride 3-bromo-2-ethyl-S-tert-pentylbenzyl Chloride 2.4-diethylbcnzyl chloride 5-bromo-2 4-dieth \'lbenzyl chloride 3-hromo-2 4-diethylbenzyl chloride 2,4-diisohutylhcnzyl chloride 5-bromo-2 4-diisobutylhenzyl chloride 7 Table IX Continued Starting Material 4-isobutyl-2-propylbcnzyl chloride Product 5-bromo-4-isobutyl-Z-propylbenzyl chloride 2,6-dipropylhenzyl chloridc 3-bromo-2,6-dipropylbenzyl chloride 4 bromo-Z.o-dipropylbenzyl chloride 2,6-diisohutylbcnzyl chloride 3-bromo-2,o-diisobutylbenzyl chloride 4-bromo-2,6diisohutylbenzyl chloride EXAMPLE 8 2 ,6-Dibrom0-4-chloromethyl-3 ,5diisopropylphenol Three hundred thirty-six parts of 2,6- dibromo-3,5- diisopropylphenol (prepared as described in Canad, J. Chem, Vol. 41, p. 1653, 1963) is allowed to react with 130 parts of chloromethylmethyl ether and 80 parts of stannic chloride in 400 parts of carbon disulfide under general conditions set forth in Organic Reactions, Vol. 1, p. 68 and 69. The reaction mixture is poured on ice, and the organic layer is separated and dried over parts of chloromethylmethyl ether and parts of stannic chloride in 400 parts of carbon disulfide under general conditions set forth in Organic Reactions, Vol. 1, p. 68 and 69. The reaction mixture is poured on ice, and the organic layer is separated and dried over anhydrous sodium sulfate. The solvent is allowed to evaporate and the residue is crystallized to give a pure sample of the title compound. Chloromethylation of the following monohaloor dihalodialkylhydroquinones or resorcinols gives the corresponding chloromethyl derivatives.

TABLE XI Starting Material Product 2bromo-3 .5diisopropylhydroquinone 5-bromo-4.6-diisopropylresorcin0l 3-bromo-5-tert-butyl-Z-isopropylhydroq uinone 3-bromo-5-sec-butyl-2-isopropylhyroquinone 3-bromo-2-isobutyl-5-isopropylhydroquinone 3-bromo-2.5 di-sec-butylhydroquinone 3-bromo-2.S-diisobutylhydroquinone 3-bromo-2,S-di-tert-butylhydroq uinone 3-bromo-S-tert-butyl-Z-isobutylhydroquinone 3-bromo-5-tert'butyl 2ethylhydroq uinone anhydrous sodium sulfate. The solvent is allowed to evaporate and the residue is crystallized to give a pure sample of the title compound. Chloromethylation of the following monohaloor dihalodialkylphenols gives the corresponding chloromethyl derivatives.

TABLE X EXAMPLE l0 1 -Bromo-2,6-diisopropy1benzene A solution of 262 parts of triphenylphosphine in 750 Starting Materials Product 2,4-dichlor0-3,6-diis0propylphenol 2,3 dichl0ro-4,6-diis0pr0pylphenol 2 ,6-dichloro-3,S-diisopropylphenol 4,5-dichloro-2,o-diisopropylphenol 2,4-dichloro-5-chloromethyl-3 6-diisopropylphenol 2,3-dichlore-5-chloromethyl-4,6-diisopropylphenol 2,6-diChlor0-4chl0romcthyl-3,5 diisopropylphenol 4 5dichloro-3-chloromethyl-2.6-diisopropylphenol 2-chl0ro-3,S-diisopropylphenol 2-chloro-3.o-diisopropylphenol 2-chloro-4,6-diisopropylphenol 2bromo-3,o-diisopropylphenol 4-bromo-3,6-diisopropylphcnol 4-chloro-2,6diisopropylphenol 3-tert-butyl-2,6-dichloro-S-isopropylphenol 3 sec-butyl-2.6-dichloro-5-isopropylphenol 2,o-dibromo-3isobutyl-S-isopropylphenol 3,5-di-sec-butyl-2.6-dichlorophenol 2.o-dichloro-3,5-diisobutylphenol S-tert-butyl-Z.6-dichloro3-isobutylphenol 3,5-di-tert-butyl-2,6-dichlorophenol 3-tert-butyl-2,6-dichloro-5-ethylphenol 2-chloro-4-chloromethyl-3.5-diisopropylphenol 2-chloro-4-chloromethyl 3,G-diisopropylphenol 2-chloro3-chloromethyl-4,o-diisopropylphenol 2-bromo-4-chloromethyl-3,6-diisopropylphenol 4-bromo-2-chloromethyl-3,6-diisopropylphenol 4-chloro-3-chloromethyl-2.6-diisopropylphenol 3-tert-butyl-2,6-dichloro-4-chloromethyl-5isopropylphenol 3secbutyl-2,6-dichloro4-chloromethyl-S-isopropylphenol 2,6-dibromo-3-isobutyl-4-chlorom ethyl-S-isopropylphenol 3,5-di-sec-butyl-2,6-dichloro-4 chloromethylphenol 2.6dichloro-4-chloromethyl-3,5-diisobutylphenol 5-tert-hutyl2,6-dichloro-4-chl0romethyl3-isobutylphenol 3.5 -di-tert-butyl-2.6dichlor0-4-chloromethylphenol 3-tert-butyl-2,6-dichloro-4-chloromethyl-S-ethylphenol EXAMPLE 9 S-Bromo-2-chloromethyl-3,6-diisopropylhydroquinone Two hundred seventy-three parts of 3-bromo-2,5- diisopropylhydroquinone is allowed to react with parts of acetonitrile is brominated with parts of propylphenol. The

65 bromine at room temperature. The solvent is evaporated and to the residue is added 178 parts of 2,6-diisomixture is heated at 200C as described in J. Am. Chem. Soc. 86, 464 (1964). The

product is distilled under reduced pressure and then fractionated at 0.1 mm Hg.

The following compounds are made by appropriate substitution in the above procedure.

EXAMPLE l2 4-Bromo-2,5-diisopropylbenzeneacetonitrile In a flask equipped with a mechanical stirrer and re- TABLE XII Starting Material Product l-chloro-2,6-diisopropylbenzene v 5-bromo-2,4-dichloro-3,o-diisopropylbcnzyl chloride 5-bromo-3,4-dichloro-2,6-diisopropylbenzylchloride 4-hromo-3,5-dichloro-2,6-diisopropylbenzyl chloride 5-bromo-2,3-dichloro-4,o-diisopropylbenzyl chloride 4-bromo-3-chloro-2.o-diisopropylbenzyl chloride 4-bromo-3-chloro-3.fi-diisopropylbenzyl chloride 3-bromo-2-chloro-4,6-diisopropylbenzyl chloride 3-bromo4-chloro-2,S-diisopropylbenzyl chloride 5-bromo-2-chloro-3,o-diisopropylbenzyl chloride 5-bro'mo-2-chloro-4,6-diisopropylbeniyl chloride 4bromo-2-tert-butyl-3.5dichloro-6-isopropylbenzyl chloride 4-bromo-2-sec-butyl-3,S-dichloro6-isopropylhenzyl chloride 3,4,5-tribromo-2-isohutyl-6-isopropylbenzyl chloride 4-bromo-2.6-di-sec-butyl-3,5-dichlorobenzyl chloride 4-bromo-3,5-dichloro-2,6-diisobutylbenzyl chloride 4-bromo-2tcrt-butyl-3.5-dichloro-6dsobutylbenzyl chloride 4-bromo-2,6-di-tert-butyl-3,S-dichlorobenzyl chloride 4-hromo-2-tert-butyl-3.5-dichlortPfi-ethylbenZyl chloride EXAMPLE 1 1 3-Bromo-2,5-dichloro-4,(u-diisopropylbenzyl Chloride A solution of 404 parts of tri-n-butylphosphine in 1200 parts of acetonitrile is chlorinated with 142 parts of chlorine at room temperature. The solvent is evaporated and to the residue is added 321.5 parts of 2- brom0-6-chloromethyl-3,5-diisopropylhydroquinone. The mixture is heated at 200C as described in J. Am. Chem. 800., 86, 464 (1964). The product is distilled under reduced pressure and then fractionated at 0.1

mm Hg.

The following compounds are made by appropriate substitution in the above procedure.

flux condenser is placed 28 parts of finely powdered sodium cyanide and 115 parts of dimethyl sulfoxide. 4- Bromo-2,S-diisopropylbenzyl chloride 145 parts) is added with good stirring, and the temperature is maintained at 65C by adjusting the addition rate of the benzyl chloride. After complete addition, the mixture is stirred for 0.5 hr at C, cooled, and diluted with 1000 parts of ice water. The reaction mixture is extracted 40 with two portions of methylenechloride. Themethylene chloride extracts are'combined and dried with anhydrous sodium sulfate. The solvent is removed under reduced pressure and the 4-brom0-2,S-diisopropylbenzeneacetonitrile distilled, bp 146C at 1 mm.

The following compounds are made by appropriate substitution in the above procedure.

5-bromoB-tert-butyl-Z-chloromethyl-oisopropylhydroquinone S-bromo-3-sec-butyl-2-chloromethyl-6- isopropylhydroquinone 5-hromo2-chloromethyl-3-isohutyl-oisopropylhydroquinone 5-bromo-3 .(w-di-sec-butyl-2-chloromethyl hydroquinone 5bromo-Z-chloromcthyl-3.6-diisobutylhydroquinone 5 -bromo-3-te rt-butyL'l-chloromethyL o-isohutylhydroquinone 5bromo-3-tcrt-butyl-2-chloromethylo-ethylhydroquinone 4-bromo-Iltcrbbutyl-Z.5-dichloro-o-isopropylbenzyl chloride 4-bromo-3see-butyL2.S-dichloro6-isopropylbenzyl chloride 4-hromo-2.S-diehloro-3-isobutyl-6isopropylbenzyl chloride 4 4-hromo-3 (i-di-scc-hutyl-2,5-dichlorobenzyl chloride 4-bromo-2 5-dichloro-3,o-diisobutylhcnzyl chloride 4bromo-3-tcrt-butyl-Z,S-dichloro-o-isohutylbenzyl chloride 4-bromo-3-te rt-butyl-2.5-dichloro-o-ethyl benzyl 4 chloride TABLE XIV-continued Starting Material 3-hromo-4-ehloro-Z,fi-diisohutylbcnzyl chloride 2 5-dihromo-3,o-diisopropylhenzyl chloride 2,5-dihromo 3,fi-di-seobutylbenzyl chloride 3.6 dibromo 2.4-ditert-hutylhen2yl chloride 4-hromo2-tert-hutyLS-chloro-S-isopropylhenlyl Product 3-bromo 4-chloro-2 6-diisobutylhcnzeneaeetonitrile 5-dihromo-3.6-diisopropylbenzeneacetonitrile dihromo-3.6-di-sec-hutylhenzc ncueetonitrilc A-di-tert-butylhenzeneacetonitrile 4-hromo-2-tert-butyl-3-chl0ro-5-isopropylbenzeneacetonitrile 4-hromo-2-sec-butyl-3-chloro-5-isopropylbenzcneacetonitrile 4-hromo-3-ehloro-Z-isohutyl-S-isopropylhcnzeneacetonitrile 3-hromo-2,5-dichloro-4.6-diisopropylhenzeneacetonitrile chloride 4-hromo-2-sec-hutyl-3-chloro-S-isopropylhenzyl chloride 4-bromo-3-ehloro-2-isobutyl5-isopropylbenzyl chloride 3-bromo-2 5-diChloro-4,6-diisopropylhenzyl chloride S-hromo-Z.4-dichloro-3,6-diisopropylbenzyl chloride romo-3 4-dichloro-Z.fi-diisopropylbenzyl chloride romo-3 5-dichloro2.6-diisopropylbenzyl chloride romo-2 5-dichloro-3 o-diisopropylbenzyl chloride romo-2,3-dichloro-4 6 diisopropylhenzyl chloride 5-hromo-2,4-dichloro-3,6-diisopropylbenzeneacetonitrile 5-bromo-3 ,4-dichloro-2 6-diisopropylbenzcneacetonitrile 4-hromo-3 S-dichloro-2,fi-diisopropylbenzeneacetonitrile 4-hrom0-l5-dichloro-3 ,o-diisopropylbenzeneaectonitrile 5-bromo-Z 3-dichloro-4fi-diisopropylbcnzeneacetonitrile When one treats bromobenzyl chloride mixtures with sodium cyanide in the above manner, mixtures of 4-bromo-3-chloro-2 o-diisopropylbenzeneacetonitrile 4-hrorno3ehloro-2. diisopropylhenzencacetonitrile 3-bromo-2-chloro-4.6-diisopropylbenzeneaceonitrile 3hromo-4-chloro-2,S-diisopropylbenzeneacetonitrile 5-bromo-2-chloro-3,o-diisopropylbenzeneacetonitrile 3-brom0-6chloro-2,4-diisopropylbenzeneacetonitrilc 4'bromo-2-chloro-3 ,5-diisopropylbenzeneacetonitrile 4-bromo-2,5-di-sec-butyl-3-chlorobenzencacetonitrile 4-bromo-3-chloro-2,5-diisobutylbenzeneacetonitrile 4-hromo-2-tertbutyl-3chloro-5-isobutylbenzeneaeetonitrile 4-hromo-Z-tert-butyl3-chloro-S-ethylbenzeneacetonitrile phy, but the mixtures themselves are useful in the herbicidal methods and compositions of this invention.

bromobenzeneacetonitriles are obtained. These can be 30 The following are examples of Conversion to halobenseparated by fractional crystallization or chromatograzeneacetonitrile mixtures.

TABLE XV Starting Material 4-bromo-5-tcrt-butyl-2-ethylhcnzyl chloride and 3-hromo-5-tert-hutyl-2-ethylbenzyl chloride 4-hromo-fi-sec-butyl-Z-ethylhenzyl chloride and 3-hromo-5-sec-hutyl-2-ethylhenzyl Chloride 4-hromo-5-( LZ-dimethylpropyl )-2-ethylben7.yl chloride and 3-brorno-5-( LZ-dimethylpropyh- 2-ethylhenzyl chloride 4-hromo-5-( LZ-dimethylpropyl )-2-propylhenzyl chloride and 3-hromo-5-( l,2-dimethylpropyl)- Z-propylhenzyl chloride 4-hromo-5-( LZ-dimethylpropyl )-2-isohutylbenzyl chloride and 3-hromo-5-( LZ-dimethylpropyh- Z-isohutylhenzyl chloride 4-hromo-5-tert-butyl-2-isobutylhenzyl chloride and 3-hromo-5tert-butyl-2-isobutylhenzyl chloride 4bromo-2ethyl-5-tcrt-pentylhenzyl chloride and 3-bromo-2-ethyl-5-tcrt-pentylhenzyl chloride 3-bromo-2,S-di-tert-butylhenzyl chloride and 4-bromo-2.5-di-tert-hutylhenzyl chloride 3-hromo-5-tert-butyl-2-ethylhenzyl chloride and 4-hromo-5-tcrt-hutyl-2-ethylbcnzyl chloride 3-hromo-5-sec-butyl-2-ethylbenzyl chloride and 4-bromo-5-sec-butyl-2-ethylhenzyl chloride 3-bromo-5-( l .Z-dimethylpropyl )-2-ethylhenzyl chloride and 4-hromo-2-( l 2-dimethylpropyl S-ethylhenzyl chloride 3-bromo-5-( l .Z-dimethylpropyl )-2-propylhem.yl chloride and 4-hromo-2-( l .Z-dimethylpropyl S-propylbenzyl chloride 3-hromo-5-( LZ-dimethylpropyl )-2-isohutylhenzyl chloride and 4-hromo-2-( L2- dimethylpropyl )-5-isohutylhen1.yl chloride Product 4-bromo-S-tert-butyl2-ethylbenzeneaeetonitrile and 3-bromo-5-tert-butyl2-ethylbenzeneacet0nitrile 4hromo-5-sec-butyl-2-ethylhenzeneacetonitrile and Il-hromo-S-sec-butyl-2-ethylhenzeneacetonitrile 4-bromo-5-( l 'l-dimethylpropyl )-2-ethylbenzeneacetonitrile and 3-bromo-5-( LZ-dimethylpropyl )-2- ethylbcnzeneacetonitrile 4-bromo-5-( l ,Z-dimethylpropyl )-2-propylbenzeneacetonitrile and 3-hromo-5-( l.2-dimethylpropyl)-2- propylbenzeneacetonitrile 4-hromo-5-( l .Z-dimethylpropyl )-2-isohutylbenzeneucetonitrile and 3-bromo-5-( l,2-dimethylpropyl)- 2-isohutylbenzeneacetonitrile 4-bromo-S-tert-butyl-Z-isohutylbenzeneacetonitrile and 3-hromo-5-tert-butyl-2-isohutylbenzeneacetonitrile 4-hromo2-ethyl-S-tert-pentylbenzeneacetonitrile and 3-bromo-2-ethyl-5-tert-pentylbenzeneucetonitrile 3-bromo-Z.5-di-tert-butylbenzeneacetonitrile and 4-bromo-2.5-di-tert-butylbenzeneaeetonitrile 3-bromo5-ten-hutyl-Z-ethylbenzeneacetonitrile and 4-bromo5-tert-butyl-2-ethylbcnzeneacetonitrile 3-bromo-5-sec-butyl-2-ethylbenzeneacetonitrile and 4-bromo-5-sec-hutyl-2-ethylbenzeneacetonitrile 3-hromo-5-( LZ-dimethylpropyl )-2-ethylben7.eneacetonitrile and 4-bromo 2-( l l-dimethylpropyl )-5- ethylbenzeneacetonitrile 3-hromo-S-( lQ-dimethylpropyl )-2-propylhenzeneacetonitrile and 4-bromo-2 l ,2-dimethylpropyl)-5-pr0pylhenxencaeetonitrile 3-bromo-5-( l ,Z-dimethylpropyl )-2-isobutylbenzeneaeetonitrilc and 4-hromo-2-( l ,2-dimethylpropyl)- S-isohutylbenzeneacetonitrilc TABLE XV-continued 3-bromo-5tert-butyl-2-isobutylbenzeneacetonitrile and 4-bromo-2-tert-butyl-5-isobutylbenzeneacetonitrile 3-bromo-2-ethyl-5-tert-pentylbenzeneacetonitrile and 4-br0mo-5-ethyL2-tert-pentylbenzeneacetonitrile 3-bromo-2-ethyl-5-t 1.1,2-trimethylpropyl)benzeneacetonitrile and 4 bromo-5-ethyl-2-( l,l,2-trimethylpropyl )benzeneacetonitrile S-bromo-Z 4-diethylbenzeneacetonitrile and 3-hromrr 2,4-diethylhenzeneacetonitrile 5-bromo-2,4-diisobutylhcnzeneacetonitrile and 3-bromo-2.4-diisobutylbenzeneacetonitrile 5-bromo-4-isobutyI-Z-propylbenzenczicetonitrile and 3-hromo 4-isohutyl-Z-propylbcnzcneacetonitrile 3-hromo-2 o-dipropylbenzeneacetonitrile and 4bromo- 2 6-dipropylbenzeneacetonitrile 3-bromo-2,o-diisobutylbenzeneacetonitrile and 4-bromo-2.o-diisobutylenzeneacetonitrile 3-bromo-2,4-diethylbenzeneacet0nitrilc and 4-hromo- 3.S-diethylbenzeneacctonitrile 3-bromo-2,4-diisohutylbenzcneacetonitrile and 4-bromo-3 ,S-diisohutylhcnzeneacetonitrile EXAMPLE 13 Part B Part A 4-Bromo-2,S-diisopropyl-a-methylbenzeneacetonitrile A mixture of 4-brom0-2,5-diisopropylbenzeneacetonit'rile (22.6 parts), 4.8 parts of a 50% sodium hydride suspension in mineral oil, and 14.2 parts of methyl iodide in 300 parts tetrahydrofuran is stirred 25 4-Bromo-2,5-diisopropyl-a,ct-dlimethylbenzeneacetonitrile When the amounts of sodium hydride and methyl iodide are doubled, and the reaction is carried out .the same way, 4-bromo-2,5-diisopropyl-a,a-dimethylbenzeneacetonitrile is obtained. By the use of Method A, the following compounds are made:

Starting Material 3-bromo-2isobutyl-5-tert-pentylbenzeneacetonitrile 5-bromo-Z,4-diisopropyl-3-nitrobenzeneaeetonitrile 5-bromo2,4,6-triethylbenzeneacetonitrile TABLE XVI Product 3-bromo-2isobutyl-oz-methyl-S-tert-pentylbenzeneacetonitrile S-bromo-Z,4-diisopropyl-cx-metlnyl-3nitrohenzeneacetonitrile S-bromo-Z.4.6-triethyl-a-methylbenzeneacetonitrile and heated at 50 for 2 hours. The reaction mixture is cooled and the tetrahydrofuran stripped under reduced By the use of Method B, the following compounds are made:

TABLE XVII Starting Material Product 3-bromo-5-tert-butyl-2-isopropylbenzeneacetonitrile 3-bromo-2,4.o-triisopropylbenzeneacetonitrile 4-bromo-5-sec-butyl-2-nitrobenzeneacetonitrile 3-bromo-5-tert-butyl-2-isopropyl-a,oz-dimethylbenzeneacetonitrile 3-bromo-2,4,6-triisopropyl-a adimethylbenzeneacetonitrile 4-bromo-5-sec-butyl-a,a-dimethyl-2-nitrobenzeneacetonitrile pressure. The solid is washed with pentane and water and dried to give 4-bromo-2,S-diisopropyl-a-methylbenzeneacetonitrile.

Alkylbenzenes can be nitrated in the same manner as described in Example 16, except that the temperature 65 is maintained at 0C. When the indicated alkylbenzenes 27 are nitrated, the resulting nitro compounds can be used for the preparation of the following anilines:

TABLE xvm 28 dition is completed, the mixture is stirred at 25C for 1 hour. It is then poured into water and ice, and the solid Starting Material Product p-diisobutylhenzene m-diisopropylbenzene p-( l ,2-dimethylpropyl )ethylhenzcne p-di-sec-hutylbenzene p-dipropylbenzene p-diisopropylhcnzenc p-isobutylcumcne p-te rt-hutylcumene p-sec-hutylcumene p-tert-pentylcumcnc EXAMPLE l4 2,5-Diisobutylaniline TABLE XIX l,4-diisohutyl-2-nitrohenzene 2,4-diisopropyll -nitrobcn1.ene 4-( LZ-dimethylpropyl l -ethyl-2-nitrobenzene 2,5-discc-butylnitrohenlene l-nitro-2,5-dipropylhcnzenc 2,5-diisopropylnitrohenlenc 2isohutyl-S-isopropylnitrohcnzene 5-tcrt-butyl-Z-isopropylnitrobenzene 5-Sec-butyl-2-isopropylnitrobcnzenc 2-is0pr0pyl- 1 -nitro-S-tcrt-pentylhenzcne filtered, washed with water and dried. The 2,6-diethyl- 4-nitroacetanilide parts) is treated with 150 parts by volume of refluxing 70% sulfuricacid solution for one hour, and the mixture poured onto ice and made basic with 5N sodium hydroxide solution. The solid 2,6-diethyl-4-nitroaniline is filtered, washed with water and recrystallized from methyl alcohol-water.

EXAMPLE l7 3,5-Diethylnitrobenzene A solution of 19.4 parts of 2,6-diethyl-4-nitroaniline in parts by volume of concentrated hydrochloric acid is diluted with'80 parts of water and added to 100 Starting Material 2,4-diisopropylnitrohcnzc ne 4-( l,Z-dimethylpropyl)-l-ethyl-Z-nitrohcnzene l-cthyl-2-nitro-4-( l 1,2,2-tetramcthyl )hcnzene 2,5-di-sec-butylnitrohenzenc l-nitro-2,5-dipropylbcnzene 2.S-diisopropylnitrobenzene Z-isohutyl-S-isopropylnitrohenzene 5-tert-hutyl-2-iso ropylnitrohenzene EXAMPLE l5 2,6-Dicthylacetanilide A solution of 74.5 parts of 2,6-diethylaniline in 200 parts of dimethylformamide is treated with 56 parts of acetic anhydride at 10C. The mixture is stirred at 40 for 1 hour, poured into ice and water and stirred. The solid 2,6-dicthylacetanilide is filtered, washed with water and dried.

Product 2,4-diisopropylaniline 5-( 1,2-dimcthylpropyl )-2-cthylaniline 2-ethyl-5-( l,1,2,2-tctramethyl)aniline 2,S-di-scc-butylanilinc 2,5-dipropylaniline 2,5-diisopropylanilinc Z-isohutyl-S-isopropylaniline 5-tert-butyl-2isopropylanilinc parts of ice. A solution of 7 parts of sodium nitrite in 15 parts of water is added and the filtered diazonium solution treated with 150 parts by volume of hypo phosphorous acid and kept cold for 24 hours. The 3,5- diethylnitrobenzene which separates is extracted with ether and distilled, b.p. l/20mm.

The following dialkylnitrobenzenes are made from the appropriate dialkylnitroanilines by the above procedure.

TABLE XX Starting Material Product 4-nitro-Z.6-dipropylaniline 2,6-diisopropyl-4-nitroaniline 2 6'diisohutyl-4-nitroaniline 2-ethyl-6-isopropyl-4-nitroanilinc Z-isohutyl 4-nitro-6propylanilinc l-nitro-3,5-dipropylbenzene 3,5-diisopropylnitrohcnzene 3,5-diisohutylnitrobenzcne 3-ethyl-5-isopropylnitrobenzene 3-isohutyll -nitro-S-propylbenzcne 3 .5-di-sec-hutylnitrohcnxcnc 3-scc-hutyl-5isopropylnitrohcnzcne 1.5-di-tert-hutylnitrohcnlcne EXAMPLE 16 I 2,6-Diethyl-4-nitroaniline A solution of 58 parts of 2,6-dicthylacctanilide in parts of glacial acetic acid and 184 parts of concentrated sulfuric acid is treated at 10 with a mixture of 19.5 parts by volume of concentrated nitric acid and 13 parts by volume of concentrated sulfuric acid. After ad- EXAMPLE l8 2,6-Diethyl-4-nitrobenzyl Chloride and 2,4-Diethyl-6-nitrobenzyl Chloride 3,5-Dicthylnitrobenzene 10 parts) is dissolved in 29 parts of chloromethylmethyl ether, and 10 parts of 60% fuming sulfuric acid is added slowly with stirring. After standing for 5 minutes. the dark hot mixture is diluted P 29 with'water and theprecipitate is filtered and dr'ied. Distillation under reduced pressure'firstgives the starting 30 dialkyl-4-nitrobenzyl chlorides using the above procedure.

TABLE XXII Starting Material Product 4-nitro-Zb-dipropylbenzyl chloride 2,6-diisopropyl-4-nitrobenzyl chloride 2.6-diisobutyl-A-nitrobenzyl chloride 2-is0butyl-4nitro-6-propylbenzyl chloride 4 2 ethyl-o isopropyl-4-nitrobe nzyl chloride 2.6di-sec-butyl 4-nitrobenzyl chloride '2.6-di-tertbutyl-4-nitrobenzyl chloride 2-sec-butyl-6-is0propyl4-nitr0benzyl chloride 3-bromo-4-nitro-2,o-dipropylbenzeneacetonitrile 3-chloro-2,6-diisopropyl-4-nitrobenzeneacetonitrile 3-bromo 2.6diisobutyl4-nitrobenzeneacetonitrile 3-iodo-2-isobutyl-4-nitro 6-propylbenzencacetonitrilc i 3-brom0-2-ethyl-6"isopropyl-4-nitrobe nzeneacetonitrile 2,6-di-sec-butyl-3-chloro-4-nitrobenzencacetonitrile 3bromo-2,o-di tert-butylA-nitrobenzcneacetonitrile 5-bromo 'Lsec-butyl-6-isopropyl-4-nitrobenzeneaceto nitrilc material and then a mixture of 2,6-diethyl-4-nitrobenzyl chloride and 2,4-diethyl-6'nitrobenzyl chloride. These are separated by chromatography and fractional crystallization.

The following dialkylnitrobenzyl chlorides are made from the appropriate dialkylnitrobenzenes by the above procedure. I

TABLE "Xx EXAMPLE 2O 3-Bromo-2,4-diethyl-o-nitrob-enzeneacetonitrile and 5-Bromo-2,4diethyl-o-nitrobenzeneacetonitrile 2,4-Diethyl-6-nitrobenzyl chloride is brominated by the procedure used to prepare 4-bromo-2-isobutyl-5 isopropylbenzyl chloride to form a mixture containing Starting Material Product l-nitro-3,5dipropylbenzene 3,S-diisopropylnitrobenzene 4-nitro-2.o-dipropylbenzyl chlo'ride 6-nitro-2,4-dipropylbenzyl chloride 2 (r-diisopropyl4-nitrobenzyl chloride Z,4-diisopropyl o-nitrobenzyl chloride g 3 5-diisohutylnitrobenzene 3-isohutyl-knitro-S-propylbenzene 2,6diisobutylM-nitrobenzyl chloride 2..4-diisobutyl-o-nitrobenzyl chloride 2-isobutyls4-nitro-o-propylhenzyl chloride 4-isobutyl-6-ni tro-lpropylbenxyl chloride 3-cthyl-5 isopropy lnitrobenzene 3.5 di-secbutylnitrobeneene 2-ethyl 6-isopropyl-4 nitrobcnzyl chloride 2-ethyl-4-isopropyL6-nitrobemy] chloride 2 6disec-hutylAmitrobenzyl chloride 2,4-di-sec-butyl-6-nitrobenzyl chloride 3.5-ditert-butylnitrobenzene 2.o-di-tert-butyl-4nitrobenzyl chloride 3-sec-butyl-5-isopropylnitrohcnzene 2-sec-butyl-6-isopropyl-4-nitrobenzyl chloride 4-sec-butyl-2-isopropyl-6 nitrobenzyl chloride EXAMPLE 19 3-Bromo-2,6-diethyl-4-nitrobenzeneacetonitrile 2,6-Diethyl-4-nitrobenzyl chloride is brominated to give 3-bromo-2,6-diethyl-4-nitrobenzyl chloride by the procedure used to prepare 4-bromo-2-isobutyl-5isopropylbenzyl chloride. 3Bromo-2,6-diethyl4-nitrobenzyl chloride is then converted to 3-bromo-2,6 diethyl-4-nitrobenzeneacctonitrile with sodium cyanide by the procedure used to prepare 4-bromo-2,5-

diisopropylbe nzeneacetonitrile. I

The 7 following. 2,6-dialkyl-3-halo-4-nitroben zeneacetonitri les are made from -.the appropriate 2,6-

3-bromo-2,4-diethyl-6-nitrobenzyl chloride and 5- bro mo-2,4diethyl6-nitrobenzyl chloride. This mixture Starting Material TABLE xxiii Product o-nitro-lfi-dipropylbenzyl chloride V I l.4-diisopropyl o nitrobenzyl chloride I 2,4-diisobutyl-b-nitrobeii:tylchloride 2 4-di-sec-butyl o-nitrbb ehzyl chloride 2.4-di tert-butyl-o nitrobcnzyl chloride 4-secbutyl-2 isopropyl-6-nitrobenzyl chloride 3-bromo-6-nitro-2 4dipropylhenzcneacctonitrile 5bromo-6-nitro 2 .4-dipropylhenzeneacetonitrile 3-bromo-2.4diisopropyl-6-nitrobenzeneacetonitrile 5-bromo-2 4 -diisopropyl-6-nitrobenzeneacetonitrile 3bromo-2.4-diisobutyl-( -nitrobenzeneacetonitrile 5bromo-2 .4-diisobutyl-6nitrobenzeneacetonitrile 2,4di-sec-butyl-3-chloro-6-nitrobenzeneacctonitrilc 2,4-di-sec-butyl-5 -chloro6-nitrobenzcneacetonitrilc 3-bromo-2,4-di-tert-butyl-onitrobenzeneacctonitrilc 5-bromo-2 4'ditcrt-butyl-6-nitrobenzeneacetonitrile 4-secbutyl'3-chloro-2-isopropyl-6nitrobenzeneacetonitrile 4:se :-butyl-5-chloro-24sopropyl-o-nitrobenzcneacetw nltrl e EXAMPLE 21 4-Bromo-2,5-diisobutyl-3-nitrobenzcneacetonitrile Starting Material 3-bromo-2,6-diisobutylhcnzeneacetonitrilc and 4-bromo2.6-diisohutylbcnzeneacetonitrile 3-hromo-2 4-dicthylbenzeneacetonitrilc and 4-hromo3 .5diethylbcnzencacetonitrilc 3-bromo-2-ethyl-5-neopentylhenzcneacetonitrile and 4-bromo-5-cthyl-2-neopentylbenzeneacetonitrile 2,5-Diisobutylnitrobenzene is treated with chloromcthylmethyl ether in the presence of 60% fuming sulfuric acid by the procedure used to prepare 2,6-diethyl-4- 25 TABLE XXIV sitions of this invention. The following are examples of the preparation of nitrohalobenzeneacetonitrile mixtures.

TABLE XXV Product 3-bromo-2,6-diisobutyLS-nitrobenzeneacetonitrile and 4-bromo-2.fi-diisobutyl-3-nitrobenzeneacetonitrile 3-bromo-2,4-diethyl-5-nitrobenzeneacetonitrile and 4-bromo-3,5-diethyI-Z-nitrobenzeneacetonitrile 3-bromo-Z-ethyl-5-neopentyl-6-nitrobenzeneacetonitrilc; 3bromo-2-ethyl-5-neopentyl-4-nitrobenzeneacetonitrile and 4-bromo-5-ethyl-2- neopentyl-o-nitrobenzeneacetonitrile EXAMPLE 22 4,5-Dichloro-2-nitro-3,6-dipropylbenzeneacetonitrile To 38 parts of 90% nitric acid is added portionwise 5parts of 3,4-dichloro-2,S-dipropylbenzeneacetonitrile at such a rate that the temperature does not exceed 50C. The solution is stirred for 2 hours at room temperature then poured into ice water. The organic phase is extracted with ether and the ethereal solution washed with water, 2% sodium hydroxide, and water. The dried ethereal solution is vacuum distilled to remove solvent and the residue is recrystallized to afford pure 4,5- dichloro-2-nitro-3,6-dipropylbenzenediacetonitrile.

By replacing 3,4-dichloro-2,S-dipropylbenzeneacetonitrile with the following benzeneacetonitriles, the following products are obtained. In some Starting Material 2.5-di-sec-hutylnitrobenzcne l-nitro-2.5-dipropylbenzene ZS-diisopropylnitrohcnlcnc Z-isobutyl-5-isopropylnitrohenzene nitrilc 5-tcrt-hutyl-2-isnpropylnitruhcnzcne nitrilc S-scc-hutyl-2-isopropylnitrohcnzcnc nitrilc Z-isopropyll -nitro-5 -tert-pentylbcnzcnc acetonitrilc Product 2.5 -di-sec-hut -l-4-chloro-3-nitrohcnzeneacctonitrile 4-hromo-3-nitro-2.S-dipropylhcnzeneacctonitrilc 4hromo-2,5-diisopropyl-3-nitrobenzcneacctonitrile 4-hrom0-2-isohutyl-S-isoprapyl-3-nitrohcnlcneaccto- 5-tcrt-hutyl-4-chloro-2-isopropyl-3-nitmbenzcneaceto- 5-sec-butyl4-chloro-2-isopropyl3 nitrohcnlcneaceto- 4-bromo-2-isopropyl-3-nitrn-5-tert-pentylhenzenc- When one nitrates mixtures of halobenzeneacetonitriles, mixtures of nitrohalobenzeneacetonitriles are obtained. These can be separated by fractional crystallization or chromatography, but the mixtures themselves are useful in the herbicidal methods and compocases nitrated isomer mixtures are obtained. These can be separated by fractional crystallization, chromatography, distillation or other techniques, but the mixtures 55 themselves are useful in the herbicidal methods and compositions of this invention.

TABLE XXVI Starting Material Product 3 ,4-dichloro-2.5-diethylhenzcneacetonitrile 3 .4-dichlnro-2.5-dipropylbenzcneacctunitrile 3 ,4-dibromo-Z.S-dipropylbcnzeneacetonitrile 3 .4-dichloro-2.5-diisobutylhenzencacetonitrile 3 ,4-dibromo-2 ,5diisohutylbcnzeneacctonitrilc 2 .5-di-tcrt-butyl3,4-dichlorohcnzcneacetw nitrilc 5-terthutyl-3 ,4-dichloro-Z-cthylhcnzcncacetunitrile 5-tert-butyl-3,4-dichloro-Z-propylbcnzeneacetonitrile 2-tert-hutyl-3.4-dichlorn-S-propylhcnzeneacetonitrilc 4.5-diehloro-3 ,o-dicthyl-Z-nitrobenzcneacetonitrile 4,5-dichloro2-nitro-3 ,6-dipropylbcnzeneacetonitrilc 4 5-dibromo-2-nitro-3,6-dipropylbenzeneacetonitrilc 4.5-dichluro-3 6diisobutyl-Z-nitrobenzeneaectonitrile 4,5dibromo-3 .6diisohutyl-2 nitrobcnzencacctonitrile 3 6-di-tcrt-butyl4 S-dichloro2-nitrobcnzeneacetonitrilc 3-tert-butyl-4.5-dichloro-6-cthyl-l-nitrohenzeneacetonitrile 3-tert-butyl4.5-dichloro-2-nitro6propylbenzeneacetonitrile 6-tcrt-butyl-4.5-dichlorwZ-nitrO-3-prop 'lhenzcncacetonitrilc 

1. THE COMPOUND 4-BROMO 2,5-DIISOPROPYLBENZENEACETONITRILE.
 2. THE COMPOUND 4-BROMO-2-TERT-BUTYL-5-ISOPROPYLBENZENEACETONITRILE.
 3. THE COMPOUND 4-CHLORO-2,5-DIISOPROPYLBENZENEACETONITRILE. 